Multi-step reaction of textile materials with multi-functional groups reactive under different catalytic conditions

ABSTRACT

Cellulosic fabrics are modified in two steps with compounds containing at least one group reactive under conditions of acid catalysis and at least one group reactive under conditions of alkaline catalysis, e.g., N-methylol acrylamides. In conducting the process, either the acid or the alkaline catalyzed reaction may be run first; the fabric may be formed into a garment subsequent to the first reaction but prior to the second reaction and an alkaline catalyst may be used which is substantially neutral on the fabric at ambient temperatures but becomes strongly alkaline at elevated temperatures.

United States Patent I CONDITIONS Inventor: Donald J. Gale, Spartanburg,

Assignee: Deering Milliken Research Corporation,

Spartanburg, S.C.

Filed: Dec. 18, 1967 Appl. No.: 694,022

Related US. Application Data Continuation of Ser. No. 244,273, Dec. 13,1962,

abandoned.

rm. Cl ..D06m 15/54, D06m 1 5/72 Field of Search ..8/1 16.3, 120; 38/144References Cited UNITED STATES PATENTS 2/1969 Baitinger ..8/1 16.3

Gale A r. 25, 1972 54] MULTI-STEP REACTION OF TEXTILE 5: magat et al. 1

MATERIALS WITH MULTI- am 1 FUNCTIONAL GROUPS REA C TIV E 3,138,8026/1964 Getchell ..8/1 16.3 UNDER DIFFERENT CATALYTIC OTHER PUBLICATIONSl-lickner et al., Journal of Organic Chemistry, Vol. 32, pp.729-733(1967) Sumrell et al., Textile Research Journal, Vol. 39, pp. 78-85 Primary Examiner-George F. Lesmes Assistant Examiner-4. CannonAttorney-H. WilliamPetry and Norman C. Armitage ABSTRACT 8 Claims, N0Drawings MULTI-STEP REACTION OF TEXTILE MATERIALS .WITIIMULTI-FUNCTIONAL GROUPS REACTIVE UNDER DIFFERENT CATALYTIC CONDITIONSThis application is a continuation of application Ser. No. 244,273,filed Dec. 13, 1962 and now abandoned.

This invention relates to novel processes for producing gar- .ments ofcellulosic materials which are characterized by a propensity forsubsequent durable settinginto any desired configuration, for example,creased, pleated, embosses and/or flat, to the fabrics from which saidgarments are made and to the garments so produced.

Cotton fabrics having varying degrees of dry and wet resiliencyproperties can be produced by a wide variety of chemical processes whichgenerally involve crosslinking the cellulose molecules of the fabricwhile the fabric is in a flat state, the wash-and-wear properties beingobtained as a result of the fabrics tendency to return to the flat stateafter distortion and/or wetting thereof, depending upon the particulartreatment given the fabric, i.e., whether the fabric has imparted to it,both dry and wet resiliency properties, or only one type. This tendencyto return to a flat state is highly desirable, but this property alsogreatly complicates the proper creasing or pleating of garments madefrom the fabric. in general, garments made from flat-set fabrics aredifficult to crease or pleat and the distorted configuration obtained isremoved from the garment by moisture. such as during laundering.

This difficulty has led to a number of cxpedients for developing theflat setting property simultaneously with the creasing or pleatingoperation, such as by spraying the garment with a cross-linking reagentand immediately thereafter conducting the cross-linking reaction whileholding the garment in the desired distorted configuration, e.g.,creased or pleated.

These processes are generally unsatisfactory in that the garmentmanufacturer must conduct the process and they are not always equippedto conduct the process under most favorable conditions. The garmentmanufacturer also must have access to special spray equipment and mustuse and keep the necessary chemical formulations in his own facilities.Furthermore, these prior procedures generally involve resins, whichrelease large quantities of noxious vapors during pressing. Also, theseprocedures generally produce only one type of resiliency properties.

It would be highly desirable if the garment manufacturer could beprovided with a fabric which he could cut and sew into garments andpress in a relatively simple manner, without any chemical treatment, toprovide a durably set configuration in addition to both wet and dryresiliency properties, Le, a fabric which is presensitized, or has apropensity, for subsequent durable setting.

It is an object of this invention to provide a fabric having apropensity for subsequent durable setting into any desiredconfiguration, such as creased, pleated, embossed and/or flat.

Another object of this invention is to produce such fabrics at the milllevel and ship them to garment manufacturers in a state whereby nofurther chemical treatment is necessary in order to provide garmentshaving both wet and dry resiliency properties and sharp creases orpleats,

Yet another object of this invention is to produce garments from suchfabrics and set these garments in the desired configuration, so thatnoxious vapors are not released, and both the desired creased or pleatedarea and the flat portions of the garment remain substantially in theirset configuration after subsequent exposure to wet conditions.

These and other objects are accomplished in accordance with thisinvention which comprises providing cellulosic material, preferablyfabric, corresponding to the general formula:

Cell O R wherein Cell is the residue of a cellulose molecule and R is anorganic .radical reactive with cellulose under catalyzed condition:impregnating the cellulosic material with a compound which catalyzes thereaction between R and cellulose at elevated temperatures. mostpreferably only at elevated temperatures, and drying the cellulosicmaterial under conditions insufficient to initiate substantial reaction.

This fabric is then shipped to the garment manufacturer while beingmaintained underconditions whereby substantial reaction of the R groupwith hydroxy groups of cellulose is precluded until after a garment isproduced therefrom. The garment is then characterized by a propensityfor subsequent durable setting in any desired configuration, merely byholding the garment in the desired configuration while subjecting thegarment to conditions whereby the system is activated for substantialreaction, whereby the R group reacts with another hydroxy group of acellulose molecule to form a stable, crosslinked garment having wet anddry'resiliency properties as desired.

The etherified cellulose produce Cell O R, which generally already hasdry or wet resiliency is preferably produced by impregnating acellulosic material with (l) a polyfunctional compound containing atleast two groups reactive with hydroxy groups of cellulose, at least oneof the groups being reactive with hydroxy groups of cellulose underconditions markedly different from the reactivity of at least one otherof the groups and (2) a catalyst for the reaction of only one of thereactive groups with hydroxy groups of cellulose. The desired etherifiedcellulose product is then produced by exposing the cellulosic materialto conditions, generally of elevated temperatures, whereby the catalyzedgroup reacts with hydroxy groups of cellulose to provide either dry orwet resiliency properties, and under which the other class of reactivegroups is substantially nonreactive with cellulose.

A cellulosic material presensitized for subsequent durable setting canthen be produced by impregnating the cellulosic material with a compoundwhich catalyzes the reaction between the remaining class of reactivegroups and cellulose at elevated temperatures and drying the cellulosicmaterial at temperatures sufficiently low that substantial reaction doesnot occur.

Upon subsequent curing, during pressing or afterwards as desired, bothwet and dry resiliency properties may be imparted to the fabric,depending on the state of swelling of the fabric at the time the lastcure step is conducted, wet resiliency properties being obtainedpredominantly on highly swollen fabrics with dry resiliency propertiesbeing obtained predominantly in an unswollen state. If the initial cureis conducted on the acid side, as when the acid-reactive group of adifunctional compound is reacted first with hydroxy groups of cellulose,and the last cure on the basic side, excellent wet resiliency propertiesare obtained at higher moisture levels. At low moisture levels,excellent dry resiliency properties are obtained. At some balancedintermediate state of swelling (and this swelling though preferablyobtained with water may be accomplished through use of other swellingagents such as organic solvents or inorganic salts), depending in eachinstance on the particular compounds utilized, a high degree of both wetand dry resiliency properties are obtained. in general, however, someimprovement in dry resiliency properties with substantial improvement inwet resiliency properties is obtained at moisture levels no greater thanabout 20 percent in excess of the regain moisture level of the fabric.For many of the reagents utilized, both wet and dry resiliencyproperties are well balanced at high levels when the total moisture inthe fabric is less than about 10 percent or when the fabric is at acomparable degree of swelling.

It should be realized, however, that regardless of the moisture levelduring the final cure, durable creases are obtained, when the fabric iscreased during the cure, with high levels of dry or wet resiliency.

Preferably, the polyfunctional compound utilized to produce the abovepresensitized fabrics and garments is one of a class of organiccompounds containing at least one terminal group reactive withhydroxy-groups of cellulose under acidic conditions and at least oneother terminal group reactive with hydroxy groups of cellulose underalkaline conditions.

The acid reactive groups are generally those found in the textile resinspresently employed in the resin treatment of cellulosic fabrics, e. g.,methylol, epoxy, acetal, alkylated methylol, aldehyde,

wherein R [S hydrogen or alkyl, -N C O, -N C S and the like. Thesegroups are characterized by their ability to combine with the hydroxygroups of the cellulose molecule under textile resin curing conditions.The term textile resin as used herein is in conformity with thegenerally accepted usage in the textile art; i. e., it defines athermosetting reagent which is applied to a textile fabric and reactedtherewith when the dry fabric is heated, usually in the presence of anacid-acting catalyst, at a temperature usually between about 140 to 200C. These latter conditions are referred to herein as textile resincuring conditions. At these temperatures, the reagent, even by itself,will ordinarily resinify in the presence of an appropriate catalyst,thus probably contributing to the use of the term resin treatment.However, it is to be understood that the term as used in the textile artis a misnomer in that in contradistinction to the generally acceptedmeaning of the term resin, textile resins are of relatively lowmolecular weights, are almost always water soluble and are oftenliquids.

Included in the class of textile resins are urea-formaldehyde and themelamine-formaldehydes, e. g., dimethylol-urea and tetra-andpenta-methylol-melamines; the acrolein-urea-formaldehyde resins; thecyclic ethylene urea-formaldehyde resins, e. g., dimethylol cyclicethylene urea and dimethylol dihydroxy cyclic ethylene urea;trimethylol-acetylene diurea and tetra-methylol-acetylene diurea; thetriazones, e. g., dimethylol-N-ethyl-triazone,dimethylol-N-hydroxyethyltriazone and N,N-ethylene-bis-dimethyloltriazone; and the urons, e. g., dimethyloluron.

These aminoplast textile resins exemplify the wide variety of structureswhich can be used to contribute an acid reactive group to thepolyfunctional compounds employed in the process of this invention.Other non-nitrogen containing textile resins can also be employed, e.g., the epoxy and acetal textile resins. It will be obvious to oneskilled in the art that the choice of compound employed to contributethe base reactive group will be influenced by the functional groupspresent in the compound contributing the acid reactive group.

The base-reactive groups are those which have the capacity of reactingwith the hydroxy groups of the cellulose molecule in the presence ofstrong base at elevated temperatures and include epoxy and halohydringroups, and-carbonyl, acetylenic, sulfone and sulfoxide activatedgroups, e. g., of the formula CH CH- .-AA wherein A is a carbonyl,sulfone, sulfoxide or acetylenic group and A is sulfatoethyl,alkali-metal sulfatoethyl, phosphatoethyl, alkali-metal phosphatoethyl,thiosulfatoethyl, and alkali-metal thiosulfatoethyl, quaternary ammoniumethyl halides, e. g., pyridinium ethyl chloride, vinyl or substituted,e. g., lower alkyl vinyl, sulfonhalide, such as sulfonfluoridechloro-Striazine and the like.

Both the acid reactive and base reactive groups can be epoxy if one ofthe epoxy groups has a lower order of activity than the other undertextile resin curing conditions so that it does not, at that step, reactwith the cellulose. Employing a mild catalyst such as, for example, zincchloride, magnesium chloride or an amine hydrochloride will facilitatesuch a preferential reaction.

Compounds which can be employed to contribute the basereactive group tothe polyfunctional compounds employed in the process of this inventioninclude polyhydroxy compounds, at least one hydroxy group of which isactivated and esterified. Esters of activated hydroxy groups can becarried through the heating step under textile resin curing conditionsand will then be available to react with the cellulose molecule in thepresence of strong aqueous base. The unesterified hydroxy group isavailable to react with the compound contributing the acid reactivegroup, e. g., an amino-plast textile resin, thereby producing apolyfunctional compound having both acid and base reactive groups.Within the above definition are included the mono-esters ofdi-B-hydroxethyl-sulfone and of di-flhydroxyethyl-sulfoxide. Themono-ester can be the sulfate, phosphate, or thiosulfate, preferably inthe form of their alkali-metal salts, or an organic ester, e. g., loweralkanoate, or other alkyl, aryl, alkaryl, or arylalkyl ester, preferablyhydrocarbon and containing from one to 12 carbon atoms.

Because of the activated character of the hydroxy groups of the startingcompounds, the mono-esters thereof can readily be prepared by employinga mole of the esterifying reagent per mole of the starting dihydroxycompound. Only very mild esterifieation conditions are required. Forexample, the sulfato mono-ester can be prepared at room temperature withabout two molar equivalents of concentrated sulfuric acid. The reactionproduct can be converted to an alkali-metal salt by pouring into icewater and then carefully neutralizing to a pH of about 4 with, e. g.,sodium carbonate.

A method of producing an alkali-metal salt directly involves mixing thestarting dihydroxy compound with about a molecular equivalent of sodiumor potassium bi-sulfate and then heating while removing the water ofreaction, usually with an azeotropic solvent. These mono-esters can thenbe reacted with an aminoplast polymethylol textile resin either prior toapplying the compounds to the selected textile material or subsequentthereto.

Examples of compounds containing acid and base-reactive groups which canbe used in the process of this invention are thereaction products of thesodium salt of the sulfate monoester of di-B-hydroxyl-ethyl-sulfone withdimethylol urea. dimethylol-N- ethyl-triazone,dimethylol-N-hydroxyethyltriazone, dimethylol cyclic ethylene urea, ordimethyloldihydroxy-cyclic ethylene urea, and the reaction products ofthe corresponding acetic acid mono-ester with each of the above textileresins.

While the above compounds are entirely suitable for use in accordancewith this invention, preferred compounds include those characterized bythe formulae:

?Hom' X is selected from sulfur and oxygen and Y is halogen, such aschlorine, bromine or iodine.

Additional suitable compounds include imides, such as Ill. X

mul thv like, whorl-in H R H I and X are as defined above. 'llm can havesubstituted therefor and sull'onium if desired.

In any of the compounds shown herein particularly those characterized byformulae I and II above, the

groups have substituted therefor it i g ll O and sulfonium if desired.Additional compounds having reactive groups of markedly different ordersof reactivity include anhydrides, such as wherein Z is an organicradical, such as and the like. The base-acting catalysts shown hereinmay be utilized to initiate the desired reactions.

Included in the above polyfunctional compounds are those wherein themethylol group is derived from aldehydes other than fonnaldehyde, suchas those derived from saturated or unsaturated aldehydes, whereby Rwould be lower alkyl, e.g., acetaldehyde; vinyl, e.g., acrolein; acetyl,e.g., pyruvaldehyde; CH CH CH, e.g., crotonaldehyde;

cg. methucrolein: OCH(CH:),\- wherein N =4, e.g.,

glyoxal (N=l): OCHtCHslnCHol-ia e.g., hydroxy adipaldehyde and the like.

Preferred compounds characterized above are the methylol acrylamides andhaIo-acetamides, e. g.,

ll H O CH N OH5C C I I=C Hz(N-methylol-N-methylacrylamide),

l 110 CIICII;NII-CC11:0Hz(N-methylmethylolacrylamid0).

ll II 0 CIIzNIIG-ClIzCl (N-methylolchloroacctamido),

and lIOClIaN CCH=CII2 The fabric is then padded with a catalyst whichcatalyzes the reaction between the ethylenically unsaturated group andhydroxy groups of cellulose only at elevated temperatures, e. g., NaHCOwhich forms strongly basic Na CO upon heating to temperatures in excessof about 65 C. After drying at lower temperatures, the fabric may beshipped to a garment manufacturer who can store the mildly alkalinefabric until ready for use, so long as activating conditions are notproduced.

Activating conditions generally arise as a result of a combination of pHof the fabric and temperature. Generally temperatures in excess of aboutC. and pH levels of 9 or greater are reached before substantial reactionoccurs.

In some instances, pH alone will initiate the reaction, e. g., as whensodiumhydroxide is utilized. If so, and this is not a preferredtechnique, retarding agents should accompany the strong base. It ispreferred, however, to utilize one of the preferred latent base-actingcatalysts set forth below. Garments can then be made from the fabric.These garments can then be folded and pressed on conventional equipment,e. g., a Hoffman press, where activating conditions are produced as aresult of the high temperature. For example, a pair of trousers Theconfiguration of the garment when reaction C. takes place, both creasedor pleated and flat or otherwise, will be substantially retained afterexposure to wet conditions, e. g., as during laundering of the garment.

in a less preferred embodiment, the procedure could be reversed, i.e.,

(1) wash, (2) dry (3) acid catalyst (4) press and cure llCell-OCHz-CHrC-NH-CHzO- Cell.

The highly preferred steam setting medium may be moist, but preferablyshould contain less than about in excess of the moisture regain level ofthe fabric, for optimum wet and dry resiliency properties. The use ofsteam greatly decreases curing and setting time.

Alternatively, the garments may be set in the desired configuration byhot, dry conditions, such as by hot-pressing without steaming, e.g., bypressing at temperatures up to about 200 C. for as long as necessary toproduce the desired reaction, e.g., less than a minute.

United States Pat. Nos. 2,837,511 and 2,837,512 disclose the reaction ofcellulose with N-methylolacrylamide and similar compounds in a two-stepoperation whereby the acidcuring groups are first monofunctionallyattached to cellulose (U.S. Pat. No. 2,837,512), after which theresulting cellulose ether is soaked in strong base solution at roomtemperature (U.S. Pat. No. 2,837,511) to produce a cross-linked product.These patents, however, are wholly deficient in disclosing apresensitized fabric, that is, an essentially dry fabric containing acatalyst for the subsequent reaction of terminal unsaturatcd groups atelevated temperatures. Also, these patents fail completely to disclosegarments made from a fabric presensitized with a latent base-actingcatalyst or suitable techniques for imparting sharp, durable creases orpleats to such garments. Furthermore, no procedure is disclosed forimparting simultaneously both wet and dry resiliency properties in acellulosic material.

The amount of acid and base reactive group containing compound which canbe employed is not critical and the exact amount to be employed depends,in part, on the properties desired in the final product and theefficiency of the selected compound. For example, amounts in the rangeof from about 1 to 40 percent, preferably about 5 to 25 percent,calculated on the weight of the dry textile material, or more or less,can be applied to the textile material as desired. As the pick-up ofsolution of the selected compound, if it is supplied as a solution, willrange from about 50 to 200 percent of the weight of the textilematerial, a solution concentration should be selected which will providethe desired deposition of compound on the selected textile materialunder the conditions of pick-up.

Although it is sometimes advantageous to apply to the textile material asingle compound having both acid-reactive and base-reactive groups inthe molecule, it is often more convenient to apply to the textilematerial a mixture of compounds which under the textile resin curingconditions or conditions employed prior thereto, is converted to acompound having the requisite acid and base-reactive groups. Forexample, a solution containing acrylamide, the desired amount offormaldehyde (generally equimolar proportions of acrylamide andformaldehyde are utilized for production of N-methylol acrylamide) andthe desired acid-acting catalyst may be prepared and padded onto thecellulosic material being treated. The acrylamide and formaldehyde mayreact in an aqueous solution of a mixture of these compounds, especiallyif heated, in which case the resulting product would fall within thedefinition of a compound having both acid-reactive and base-reactivegroups in the molecule.

Alternatively, the fabric may first be impregnated with a conventionalacid-reacting textile resin and a suitable acidacting catalyst and curedafter which a base-reacting crosslinking reagent and a suitable latentbase-acting catalyst are applied to the fabric. After drying underconditions insufficient to initiate substantial reaction between thecross-linking reagent and hydroxy groups of cellulose, the fabric may beshipped and made into garments which can be pressed and cured to obtaindurable configurations as desired, along with improved wet and dryresiliency properties.

This procedure can be reversed so that the basic cure can be conductedinitially followed by impregnating ofthe fabric with a textile resin andlatent acid-acting catalyst. In any of the procedures of this invention,where optimum storage and an optimum degree of wet resiliencyproperties, along with dry resiliency properties, are desired, the finalcure should be on the basic side, i.e., the fabric supplied the garmentmanufacturer already has been reacted on the acid side.

in another procedure, the fabric may be impregnated with theacid-reacting textile resin, an acid-acting catalyst and a base-reactingreagent which does not volatilize during the curing under textile resincuring conditions. Suitable nonvolatilizing base-reactive compoundsinclude XH Cl-l CSO CH CH X, wherein HX is volatilized only under basicconditions, e.g., NaO SCH CH SO CH CH SO Na and dihydroxyethyl sulfone;

methylene-bis-acrylamide, and the like.

In yet another embodiment of this invention, single compounds containingboth acid-reactive and base-reactive groups may be combined with any ofthe textile resin formulations set forth herein. For example, theN-methylol acrylamide or chloroacetamide may be combined with aconventional triazone resin to provide a sometimes better performingproduct, though of course, less economical.

The textile resin catalysts employed during the heating step undertextile resin conditions are well-known class of compounds and includethe acid-acting" compounds, i.e., those compounds which are acidic incharacter under the curing conditions. The most common are the metalsalts, e.g., magnesium chloride, zinc nitrate, and zinc fluoroborate,and the amino salts, e.g., monoethanolamine hydrochloride and 2-amino-2-methyl-propanol nitrate. The amounts of catalyst to be employedare the same as those employed when using the usual textile resins,e.g., up to about 20 percent by weight of the acid-reacting compoundemployed, with the preferred range being from about 0.5 percent to about10 percent.

While any acid-acting catalyst may be utilized, it may be preferable insome instances to use a mild or strong catalyst depending on thepolyfunctional compound. For example, if both the acid-reactive andbase-reactive groups are epoxides, it is preferred to use a mildacid-acting catalyst to induce the required preferential reaction. Onthe other hand, when utilizing N-methylol acrylamide, it is oftenpreferred to utilize a strong acid-acting catalyst, such as zinc nitrateand the like in that improved properties, such as less chlorineretention, are obtained using the stronger acid catalysts. In thisregard, compounds like zinc nitrate, which produce relatively low pHvalues in the fabric during curing, are considered strongly acidic,whereas compounds like magnesium chloride are considered mildly acidic.

Selection of the base-acting catalyst is particularly critical for theproduction of a presensitized fabric which will withstand normalstorage. The base-acting catalyst is pH of compound which 'does notinitiate substantial reaction between the base-reactive group andhydroxy groups of cellulose under normal conditions, but does initiatesubstantial reaction under prescribed conditions, such as elevatedtemperatureor some other activating means, as by use of another chemicalcompound. For example, an alkali-metal sulfite can be padded onto thefabric and be decomposed into strongly basic alkali-metal hydroxide byincluding small amounts of formaldehyde in the steam used for curing.The latent baseacting catalyst utilized herein, however, preferablycomprises alkaline-earth salts, such as alkali-metal carbonates likesodium bicarbonate, which is neutral to mildly alkaline, e.g., pH ofabout 8.5, on the fabric but decomposes at temperatures in excess ofabout 80 C. to form the stronger base sodium carbonate, which willinitiate substantial reaction at the elevated temperatures utilizedduring press-curing. Sodium carbonate may be utilized if desired, sincethe pH of 9.5 in the fabric produced by this compound under normalconditions is generally insufficient to initiate the desired degree ofreaction to any appreciable extent under normal temperature conditions.Fabrics at pH levels above about 10, however, gradually degrade duringstorage and essentially neutral or mildly alkaline catalysts arepreferred where storage properties are desired.

Additional base-acting catalysts include potassium bicarbonate,potassium carbonate, sodium silicate, alkali-metal phosphates, such assodium or potassium phosphates; barium carbonate; quaternary ammoniumhydroxides and carbonates, e.g., lauryl trimethylammonium hydroxide andcarbonate, and the like.

These bases are usuallyemployed as about 0.2 percent to about .16percent solutions, preferably about 2 percent to about l6 percent. Theexact concentration, while not critical, will affect the resultsobtained. Theconcentration which gives the optimum result will depend,in part, on the percent pickup of the base by the textile material, thetemperature at which the reaction is conducted, and the amount of baseconsumed in the reaction. If a highly acidic group is released duringthe reaction, the amount of base applied to the textile material shouldbe at least the amount that will be consumed by that group. Generally, a3 percent to 10 percent aqueous solution of base is preferred when thepick-up is between about 30 percent to I30 percent, calculated on theweight of the dry textile material. In carrying out the initial heatingstep of the process of this invention the cellulosic material, uniformlyimpregnated with a polyfunctional organic compound having at least oneacid reactive group and at least one base reactive group is heated undertextile resin curing conditions in the presence of an acidic catalyst.As stated before, this acid and base reactive compound can be that whichis initially applied to the textile material or can be the product of anin situ reaction of an acid reactive group containing compound and abase reactive group containing compound. Under ordinary conditions, thisstep employs conditions identical to that of a conventional resintreatment. For example, the selected reagents can be applied to thetextile material by padding, spraying, or applicator roll and thenpassing through squeeze rolls, if necessary, to achieve the desiredpick-up of the reagents. As these reagents are ordinarily applied asaqueous solutions, the textile material is dried and then heated to theappropriate temperature, e.g., about 100 to 200 C., preferably about 140to l90-C., to fix the compound to the textile material. When employingfabric these steps of drying and curing are conducted while the fabricis free from extraneous wrinkles, usually in a smooth, open widthcondition.

Conventional curing equipment is suitable for this operation. Forexample, when employing a fabric, the reagents can be applied with theusual equipment and then passed through squeeze rolls and dried, e.g.,at room temperature or while the fabric passes through a hot air oven orover heated cans. in

production, it is preferred to conduct the heating operations in atenter frame to maintain the desired dimensions.

The thus treated textile material is then ordinarily given a thoroughwash to remove the catalyst and any unreacted reagents. lf sufficientreagents are employed in this step, the textile material will be foundto possess a high degree of dry resiliency at this stage.

The step of contacting the textile material with the desired base-actingcatalyst employs conditions generally employed in the textile trade, andthe necessary techniques will be apparent to those skilled in the art.For example, impregnating the textile material with the selectedcatalyst can be accomplished in a manner similar to those employed inthe previous step. The material can be moistened by dipping in anaqueous solution of the selected base, and squeezed through rollers toachieve the desired pickup of the base.

The fabric is then dried under conditions insufficient for thebase-acting catalyst to initiate substantial reaction between thebase-reactive group and hydroxy groups of cellulose. The fabriccontaining the latent catalyst is then shipped to garment manufacturersfor production of garments which can be subsequently pressed to obtainboth wet and dryresiliency properties, in addition to sharp, durablecreases or pleats.

When the base reactive step is conducted first, strong aque-- ous baseshaving a pH of at least 10 as a 1 percent aqueous solution arepreferably utilized. The bases most commonly employed are thealkali-metal hydroxides, although other compounds such as sodiumsilicate, sodium carbonate, and potassium carbonate can also beemployed. These bases are usually employed as about 0.2 percent to about16 percent solutions, preferably about 2 percent to about 16 percent.The exact concentration, while not critical, will affect the resultobtained. The concentration which gives the optimum result will depend,in part, on the percent pick-up of the base by the textile material, thetemperature at which the reaction is conducted, and the amountof baseconsumed in the reaction. if a highly acidic group is released duringthe reaction, e.g., when employing a sulfato ester-containing compound,the amount of base applied to the textile material should be at leastthe amount that will be consumed by that group. Generally, a 3 percentto 10 percent aqueous solution of base is preferred when the pick-up isbetween about 30 percent to percent, calculated on the weight of the drytextile material.

A latent acid catalyst, for example, any of the above recited catalystscan be then padded onto the cellulosic material, though preferably amild catalyst is applied. After drying under conditions insufficient toproduce substantial reaction between the acid-reactive group and hydroxygroups of cellulose, a presensitized fabric is obtained. Garmentsproduced from these fabrics can be durably set by pressing under textileresin curing conditions. Storage time and wet resiliency properties willgenerally be lower in this embodiment of the invention.

Textile materials which can be treated according to the processes ofthis invention are those in which the anhydroglucose units arechemically substantially unmodified. Thus, the term cellulosic textilematerial" when used herein means any textile material comprising fiberswithin the above definition, e.g., cotton, paper, linen, jute, flax,regenerated cellulose fibers, including viscose rayon, in the form ofstaple, yarn and fabrics. This invention is directed primarily andpreferably to cellulosic textile fabrics, either knitted or woven,preferably woven. However, the advantages of this invention can beachieved by treated the cellulosic fibers, yarns, or threads employed toproduce these fabrics. The thus treated material, when woven or knittedinto fabric will produce a fabric having better wet and dry resiliencythan identical fabric woven from identical untreated yarn or thread.Moreover, the properties of the staple yarn and thread are modified in adesirable fashion. For example, the staple is less prone to compressioninto hard masses during wet or dry processing.

Satisfactory results can be achieved employing cellulosic materialscontaining both cellulosic and non-cellulosic fibers,

especially if the non-cellulosic fibers have minimum carecharacteristics of their own. For example, the wet and dry resiliency offabrics formed from a mixture of polyester, such as polytethyleneterephthalate), polyamide such as poly(hexamethylene adipamide) oracrylic fibers, such as polyacrylonitrile and copolymers containing atleast about 85 percent combined acrylonitrile filaments or fibers withcotton or rayon can be improved by this process. Obviously, if thenon-cellulosic fibers have low minimum care characteristics, theimproved characteristics of the materials treated according to theprocesses of this invention will be more readily apparent when thecellulosic content of the fabric is substantial, e.g., about 40 percentor more by weight. As stated above, the invention is primarily directedto fabrics, preferably consisting essentially of cellulosic materials,especially cotton. Bleached and usually also commercially mercerized orprinted fabric, e.g., printcloth, broadcloth, and oxfordcloth, isusually employed as the starting fabric.

After the initial curing step, the cellulosic material preferablycontains at least about 1.8 unsubstituted hydroxy groups and at least0.05 hydroxy groups per anhydroglucose unit substituted through an etherlinkage by a radical having a terminal grouping reactive towards hydroxygroups of cellulose. 1n the usual instance, as where the acid-reactivegroup of the polyfunctional compound is reacted first, the substituentis base-reactive.

Such degree of substitution is preferred for the desired cross-linkingreaction to take place to a satisfactory extent. Preferably, there areat least two unsubstituted and, more preferably, at least 2.5unsubstituted hydroxy groups per anhydroglucose unit for the samereason. Of the remaining hydroxy groups, an average of at least 0.05,more preferably 0.2-0.5 hydroxy groups per anhydroglucose unit issubstituted through an ether linkage to one of the R groups set forthabove.

In addition to the preferred number of free hydroxy groups and reactiveradical-substituted groups, the cellulosic material can have a minorproportion of hydroxy groups substituted with ether or ester groups,e.g., lower-hydrocarbon esters including the acetate, propionate,butyrate, benzoate, sulfate, phosphate, aryl and alkyl esters; and loweralkyl ethers including methyl and ethyl; and hydroxyalkyl, such ashydroxyethyl and carboxymethyl ethers.

In some instances, the addition of reducing agents, such as alkali-metalborohydride, such as sodium and potassium borohydride; alkanolaminesulfites, such as monoethanolamine sulfite, monoisopropanolamine sulfiteand others containing up to about eight carbon atoms in the alkyl chainand the like can be applied to the cellulosic material being treated toinhibit any yellowing which may tend to occur under setting conditionsin the garment state. Furthermore, when sodium borohydride is appliedalong with sodium bicarbonate or sodium carbonate, the time of pressingon the Hoffman press is reduced, e.g., to 30-60 seconds with noyellowing of the fabric when steam is used, whereas without steam asmuch as 5 minutes would be required to get the same result. Durablecreases are also produced in as little as seconds using a hot platenpress at 350 F.

Preferred embodiments of the present invention are shown in thefollowing Examples.

EXAMPLE I The physical properties of the fabrics treated according tothe process of this invention were determined according to acceptedstandard methods. Tear strength was determined by A.S.T.M. Testdesignation D-l424-59. Tensile strength was determined by A.S.T.M. Testdesignation D-39-59 (No. 10). Crease recovery angle was determined byA.S.T.M. Test designation D 1295-53 T. See "A.S.T.M. Standards forCommittee D-13 on Textiles," (1959). Flat dry ratings were by A.A.T.C.C.Test designation T-88-l958.

Preparation of N-methylolchloroacetamide:

Eighty-one gms. of a 37 percent formaldehyde solution (1 mole) areadjusted to a pH of 8.0 by the addition of l N-sodium hydroxidesolution. To the solution are added 93.5 gms. 1 mole) of2-chloroacetamide. The mixture is heated for 1 hour at 60 C. with theconcomitant addition of l N-sodium hydroxide to maintain the pH in therange 6-8. Towards the end of the heating period. 240 gms. of water areadded. After cooling, the clear solution weigh 435 gms. and thereforecontain 28.4 percent by weight of N-methylolchloroacetamide.

EXAMPLE u The N-methylolchloroacetamide solution of Example 1 is appliedto X80 bleached and mercerized cotton print cloth in the followingmanner. The print cloth is padded through a solution comprising 10percent solids N-methylolchloroacetamide, a zinc nitrate catalyst (1% OFZn(NO,,). ,(H O), 6 percent of a polyethylene softener (Moropol 700) and/'i percent of the surfactant (Surfonic N-95). The wet fabric is thensqueezed through nip rolls at 60 lbs. per square inch pressure toprovide a pick-up of about 75 percent based on the weight of the dryfabric. The fabric is dried over hot cans and then cured by passingthrough a curing oven about 175 C. for seconds.

The cured fabric is then washed to remove all unreacted chemicals, airdried and padded and squeezed to 75 percent pick-up with 5 percentaqueous solution bicarbonate. The fabrics are then air dried to give thepresensitized cotton fabric.

The presensitized fabrics so produced give sharp creases substantiallydurable to laundering when pressed while steaming on the Hoffman pressfor 1 minute. In addition, good wet and dry resiliency properties areproduced.

EXAMPLE Ill The procedure of Example 11 is repeated except that aqueoussolutions containing 1 percent, 3 percent 5 percent and 7 percent sodiumcarbonate, respectively are substituted for the sodium bicarbonatecatalyst. Essentially the same results are obtained as before, with bestresults being obtained with the 3 percent solution.

This procedure is again repeated, except that the fabric swatchesimpregnated with sodium carbonate are dried over hot cans, heated to 110 C. Under these conditions, the fabric does not reach the temperatureof the hot cans so that the reaction between the acetyl halide groupsand hydroxy groups of cellulose does not occur to a degree sufficient todestroy the fabrics propensity for subsequent durable setting. Uponpressing on a Hoffman press for 2 minutes as before, sharp creasessubstantially durable to laundering are obtained, with good wet and dryresiliency properties.

EXAMPLE lV Samples of the same starting fabric as that described inExample ll are padded in the manner described therein with a solutioncomprising 15 percent ofa 60 percent aqueous solution ofN-methylolacrylamide (obtained from the American Cyanamid Company), 2percent catalyst AC (a solution of 2- amino-2-methyl-l-propanolhydrochloride), 6 percent of a polyethylene softener (Moropol 700) and/a percent of a surfactant (Surfonic N-). The fabrics are dried over hotcans, then cured by passing through a curing oven at 182 C. for 90seconds. After washing and drying, the fabrics exhibit a tensilestrength of 27.6 lb. a tear strength of456 gm., crease recovery angles(warp and fill) of 210 (dry) and 230 (wet), and spin and tumble ratingsof 1.7 and 2.8, respectively.

The fabric samples are further padded to a pick-up of approximately 85percent, with 4 percent aqueous sodium bicarbonate and 2 percent aqueoussodium carbonate and air dried to give the presensitized cotton fabrics.

The presensitized fabrics yield crease or creases durable to launderingwhen pressed on the Hoffman press in the presence of steam for 3minutes. The creaseshave a good appearance irrespective of whether thefabrics are spun dried followed by line drying, or tumble dried. Thesodium carbonate catalyst gives slightly better creases than the sodiumbicarbonate.

EXAMPLE V Samples of the starting fabric of Example ll are padded asdescribed therein with r a solution comprising N methylolacrylamidepercent or percent ofa 60 percent solution, being equivalent to 9percent and 15 percent solids, respectively), 3 percent catalyst AC, 6percent Moropol 700 polyethylene softener and /:i percent Surfonic N-95surfactant. After drying over hot cans, the fabrics are cured at 182 C.for 90 seconds, washed and dried.

EXAMPLE VI Padding of the samples prepared in Example V to a pick-up ofabout 85 percent with aqueous solutions containing 4 percent sodiumbicarbonate and 3 percent sodium carbonate together with Va percentsodium borohydride, followed by airdrying, yield presensitized fabricswhich are given durable pleats'or creases in the presence of steam inthe Hoffman press. The presence of the sodium borohydride completelyeliminated any tendency of the fabrics to yellow during the pressingoperation. However, the pressing time for production of a good durablecrease is now only -60 seconds.

It may be noted that the fabrics impregnated with sodium bicarbonatesolutions must be dried at less than 65 C. to avoid conversion of thebicarbonate to carbonate. The fabrics impregnated with sodium carbonatesolutions may be dried over hot cans at temperatures up to 110 C., sincethis temperature time is insufficient to cause the vinyl group to reactwith the cellulose.

Good durable creases are also imparted to these presen sitized fabricson the Hoffman press in the absence of steam if the pressing time wasextended to 5 minutes.

Good durable creases are also produced on a hot Platen press l77 C.) in15 seconds with virtually no yellowing.

Good durable creases are also produced by pressing the samples in thepresence of steam on the Hoffman press for 5 seconds, followed bysetting in dry air in an oven at 160 C. for 2 minutes. The bicarbonatecatalyzed samples have 4.0 X 4.0 spin and tumble ratings after thislatter press-curing operation.

EXAMPLE VII The examples thus far enumerated have involved theproduction of presensitized fabrics by the acid-catalyzed reaction, withthe cellulose hydroxy groups, of one functional group in a difunctionalreagent. The second functional group is then subsequently reacted underconditions of basecatalysts. It is also possible to reverse thisprocedure as the present example will show.

The starting fabric of Example II is padded as described therein withsolutions comprising N-methylolacrylamide (9 percent or 18 percentsolids) and 3 percent sodium hydroxide. After ageing overnight at roomtemperature, the fabrics are washed and dried, and at this point exhibitspin and tumble ratings both equal to 1.0. The fabrics are then paddedto about 85 percent pick-up with a magnesium chloride catalyst (catalystMX; 2 percent or 3 percent and air-dried. The

presensitized fabrics thereby obtained are given creases durable tolaundering by pressing on a Platen press at 177 C. for. 60 seconds. Noyellowing of the fabrics occurred. Similar results are obtained withcatalyst AC.

EXAMPLE Vlll This example illustrates the use of a difunctionalpresensitizing agent where advantage is taken of the very differentreactivities of the two cpoxide groups contained therein. In this case,both steps in the process involve acid catalysts.

The starting fabric of Example II is padded as described therein with asolution containing 20 percent of vinylcyclohexene diepoxide and 2% zincfluol'oborate (Zn(BF4)z and dried at a temperature of 140 C. The fabricis washed, dried, repadded to about 85 percent pick-up with 1.5 percentZn(BF and dried, to yield the presensitized fabric.

Durable creases are imparted to this fabric by pressing in the Platenpress at a temperature of 177 C. for 60 seconds.

EXAMPLE IX therein with a solution comprising 20 percent of the abovesolution, an acid catalyst (1 percent Zn(NO,,) .6l-l 0), or 2 percentcatalyst MX) 6 percent Moropol 700 polyethylene softener and /3 percentSurfonic N- surfactant. After drying over hot cans, the fabrics arecured at l77 C. for 90 seconds, washed and dried.

These fabrics are padded to approximately percent pick-up with asolution comprising 4 percent sodium bicarbonate and 0.2 percent sodiumborohydride, and air dried to give the presensitized fabrics. Sixtyseconds pressing in the presence of steam on the Hoffman press issufficient to impart moderately good creases to the presensitizedfabrics, which are durable to laundering.

EXAMPLE X The procedure of Example IX is repeated except that thereaction product of 1 mole acrolein and 3 moles acrylamide, condensed atpH 2 by heating at 60 C. for 30 minutes, is utilized as thepresensitizing agent. The fabric is padded with a 50 1 percent solution(adjusted to pH 9) of the reaction product containing 3 molesformaldehyde. Substantially similar results are obtained.

EXAMPLE XI The procedure of Example ll is repeated except that anaqueous solution containing 10 percent of the sodium salt of the sulfatomono-ester of di-B-hydroxy-ethyl-sulfone, 10 percent dimethylol ureaalong with the same catalyst, softener and surfactant. Substantiallysimilar results are obtained.

EXAMPLE XII The procedure of Example IV is repeated except that 5percent hydroxyethyl triazone is added to the initial treating solution.The pressed products are characterized by higher strength properties andbetter tumble ratings.

Iclaim:

l. A process for producing a durable Press garment which comprises a.impregnating a cellulosic textile fabric with a polyfunctional, organiccreaseproofing compound having at least one vinyl group or a precursorthereof and at least one N methylol group and an alkaline catalyst whichis substantially neutral on the fabric but becomes strongly alkaline attemperatures in excess of 80 C;

b. reacting said creaseproofmg compound and hydroxy groups of celluloseto form an ether linkage therebetween;

comprises ,a. impregnating a cellulosic textile fabric with (l) apolyfunctional, organic creaseproofing compound selected from the groupconsisting of and wherein R is selected from the group consisting ofhydrogen, lower alkyl; R is selected from the group consisting ofhydrogen and lower alkyl; R is selected from the group consisting ofhydrogen and methyl; X is selected from the group consisting of sulfurand oxygen; R is selected from the group consisting of -CH CH and and Yis a halogen; and (2) an acidic catalyst;

b. reacting said creaseproofing compound and hydroxy groups of celluloseto form an ether linkage therebetween;

c. thereafter impregnating said cellulosic textile material with analkaline catalyst which is substantially neutral on the fabric butbecomes strongly alkaline at temperatures in excess of C;

d. drying said fabric at a temperature insufficient to initiatesubstantial reaction e. cutting said fabric into garment sections;

f. sewing said sections to form a garment;

g. pressing said garment in a desired configuration; and

h. subjecting said garment to conditions whereby said impregnated fabricis activated for substantial reaction to form a stable, crosslinkedgarment.

3. The process of claim 2 wherein during the final curing the moisturelevel of the fabric is maintained below about 20 percent in excess ofthe regain moisture level of said fabric until after the crosslinkingreaction has occurred.

4. The process as defined in claim 2 wherein the pressing step and thereaction step are conducted simultaneously,

5. The process as defined in claim 2 wherein the polyfunctional compoundis N-methylol acrylamide.

6. The process as defined in claim 2 wherein the polyfunctional compoundis N-methylol haloacetamide.

7. A cellulosic textile fabric produced according to the process ofclaim 1.

8. A cellulosic textile fabric produced according to the process ofclaim 2.

2. A process for producing a durable press garment which comprises a. impregnating a cellulosic textile fabric with (1) a polyfunctional, organic creaseproofing compound selected from the group consisting of wherein R1 is selected from the group consisting of hydrogen, lower alkyl; R2 is selected from the group consisting of hydrogen and lower alkyl; R3 is selected from the group consisting of hydrogen and methyl; X is selected from the group consisting of sulfur and oxygen; R5 is selected from the group consisting of -CH2CH2- and and Y is a halogen; and (2) an acidic catalyst; b. reacting said creaseproofing compound and hydroxy groups of cellulose to form an ether linkage therebetween; c. thereafter impregnating said cellulosic textile material with an alkaline catalyst which is substantially neutral on the fabric but becomes strongly alkaline at temperatures in excess of 80* C; d. drying said fabric at a temperature insufficient to initiate substantial reaction e. cutting said fabric into garment sections; f. sewing said sections to form a garment; g. pressing said garment in a desired configuration; and h. subjecting said garment to conditions whereby said impregnated fabric is activated for substantial reaction to form a stable, crosslinked garment.
 3. The process of claim 2 wherein during the final curing the moisture level of the fabric is maintained below about 20 percent in excess of the regain moisture level of said fabric until after the crosslinking reaction has occurred.
 4. The process as defined in claim 2 wherein the pressing step and the reaction step are conducted simultaneously.
 5. The process as defined in claim 2 wherein the polyfunctional compound is N-methylol acrylamide.
 6. The process as defined in claim 2 wherein the polyfunctional compound is N-methylol haloacetamide.
 7. A cellulosic textile fabric produced according to the process of claim
 1. 8. A cellulosic textile fabric produced according to the process of claim
 2. 